Glycol ether



{@naart'sur :o-FFicET 1 .H i 6,576 a I Gar-col. E'rnER-jf cal-am H.Coleman; Lindley awe, and Game VrMoore, Midland, Mich, assigncrs to TheDow Chemical Company, Midland, Mich, a corporation of Michigan LNDrawing. 'Application.December 16, 1938," r Serial No..1246,134 v6Claims. romeo-61a I This inventionaconcerns certain new glycol ethersand a method of making same.

, In our (lopending an no tion Serial No.

90,380, filed July 13, 1936, of which the present application is-acontinuation-inpart,,we have general formula,

disclosed a. .class of new' glycol ethers having. the

wherein the xenyl, i; erdiphenyl radical, may

contain neutral substituents such ashalogen or bon atom, which xenoxyradical may'alsogcontain neutral substituents I In the, co-pending callyas xenyl-glycol ethers. I I

' In said co-pending application Serial No.

90,380 a method of preparing the 'xe nyl glycol ethers is given and itis shown that twotypes of tion, be referred to generically as fxenylglycol ethers, and the dixenyl ethers of glycols herein claimed will bereferred to ,v as "dixenyl glycol ethers.

formula,

wherein}? representsihydrcgen or'an alkyl group .ing a .dihalo-aliphatic hydrocarbon to a reaction alkyl groups, R. representshydrogen or an alkyl group and Y. represents a halogen or xenoxy.radical attached to a primaryor secondary C311",

application such ethers are referred togeneri- I such ethers; via, amonoxenyl ether offa chloro aliphatic hydrocarbon anda dlxenyl ether ofawhenwater-or alcohol is used as a reaction me-. dium, the hydroxide ispreferably employed in v a proportion notgreatly exceeding that requiredThe dixenyl glycol "ethers havethe general,

7 I per mole of the dihalo-aliphatic hydrocarbon reactant. 1

. land the renyliradicals may contain neutral sub.-

stituentsss'uch. as halogen or alkyl groups and n is integer 'I'heykare, useful as plasticizing agents in lacquersand varnishes and innitrocellulose,,cellulose acetate, and cellulose ether compositions,fI'hey"may also be employed as chemical agents for. the preparation of avariety of organic. c mpounds.

The xcnyl -glycol' ethers are: preparedby: heat-' temperature withw ametal xenate (ora mixture of a xenol and a metal hydroxide) inthe'pres'-' -ence1or absence of a reaction-medium, such as water;alcohol, benzene, etc. The dihalo-aliphatic hydrocarbon reactant isa'satu'rated com-- pound containing chlorine 'and/or bromine as thehalogen substituents, the latter being at- I tached, to two differentprimary or secondary carbonatoms. Among the various 'dihalo-ali phatichydrocarbons which may be employed are 0 ethylene chloride, ethylenebromide, l chloro- Z-bromo-ethane, propylene chloride,1',3-dichlbro-propane, i1-=chloro-3Jerome propane, 1,3-dichloro-isobutane, 1';=3'--'dibromo-bu'tar 1e, 1,4-di-.-.ch'loroebutane; -a normal-butyle'ne chloride, a

- normal-hexylene chloride, etc. .The metal hydroxideeor ,xenate ispreferably an alkali metal compound, e. g. a sodium or potassiumcompound, although corresponding compounds of other metals, e.g. calciumorbarium, can be used. The reactants may be employed in any desiredproportions, but for sake of economy and to avoid side reactions whichmay occur, especially to form a salt of the xenol. When a mono-xenylether of a halo-aliphatic hydrocarbon is the product desired,jonegmoleculan equivalentor ,-more of the dihalo-aliphatic hydrocarbonreactant, isprei erably employed per mole of xenol. 'When adixe'nyl'ether of aglycol is desired approximately twomolesof a xenoL-oran equivalent amount of a metal xe'nate, is preferably usedfI'hehreaction usually occurs smoothly at temf l perature's between: andf C.,,butmay be carried outat considerably higher temperatures,

e. g. 200? (3., if desired. It may be effected by 60 V the particularreactants employed, the temperature at which the reaction is carriedout, etc.

The ether product is separated'by conventional procedure, e. g. bydistillation of the reacted ,1

mixture. I

The following examples describe anurnber of I a ways in which theprinciple of the invention has been applied, but are not to be construedas limiting the invention.

' xenol, 564 grams (3 mols) of ethylene bromide,

123.2 grams (3.08 mols) of sodium hydroxide, and 751 grams of water washeated under re.

, Example 1 A mixture of 510 grams. (3 mols) of orthoflux attemperatures varying from 86 to 100 C. for 1.5 hours. The mixture wasthen cooled, neutralized with sulphuric acid, and the'organic' layerthereof was separated and distilled; There were obtained 302 grams (1.74mols) of unreacted ortho-xenol, 296 grams (1.07 mo1s)"of 1-bromo-2-(ortho-xenoxy-) ethane, and 25.6 grams (0.07 mol) of1,2-di-(ortho-xenoxy-) ethane. The yields of 1-bromo-2-(ortho xenoxy-)ethane and 1,2-di- (ortho-xenoxy-) ethane, based onthe ortho-x'enolreacted, were 84 .7 per cent and 0.6 per cent of theoretical,%respectively. The 1-- bromo-2(ortho-xenoxy-) ethane is a white crys-:

talline compound melting at 665 boiling at approximately 170 to 175 C.under 5 millimeters I pressure, and having the formula,

' and 450 cubic centimeters of benzene was heated The 1,2-di- (ortho-xenoxy-) ethane product, a white crystallinecomp'ound melting at 100.5?C'.,

boiling at about 268 C. under 5 millimetersvpressure, and having theformula, I

Example 2 p, I A mixture of 510 grams (3 mols) of orthoxenol, 148.5grams,(1.5' mols) of ethylene chloride, grams (3 mols) of sodiumhydroxide,

to C. in a rotating bomb for 4 hours. The bomb was then cooled and thecharge removed.

The mixture wasacidified by treatment with a dilute sulphuric acidsolution, washed thoroughly with. water and distilled. There wereobtained.

253 grams (1.49 mols) of unreacted ortho-xenol,

chloro-2- (ortho-xenoxy) 56.6 grams (0.243 moly'of "1-chloro- 2 -(ortho-.xenoxy-Y ethane and 197.5 grams (0.54 mol) of1,2-di-(ortho-xenoxyethane. ,The yields'of I I ethane and. 1,2;di-(ortho-xenoxy-) ethane were 16.2 percent and 76 per cent of theoretical,respectlvely,' based on the ortho-xenol reacted.

Example 3 Amixture of 510 grams (3 mols) of ortho- Xenol, 594 grams (6mols) of ethylene chloride, and 240 grams (6'mols) of sodium hydroxidewas heated for about 15 minutes in a rotating bomb attemperatures whichrosemspontaneously from about 150 C. to 205 C. during said period. The

bomb was then cooled, thecharge removed, and

-' "the products separated as in Example 2. There were obtained, 128grams (0.75 mol) of unre- "acted'ortho-xenol, 312 grams(1.34 mols) of 1-,chloro-2-(orthoxenoxy) ethane, and 126 grams (0.34. mol) of1,2'-di'-(ortho-xenoxy-) ethane. The yields of1-.chloro-2-(ortho-Xenoxy) ethane and l,2"-di-(ortho-xenoxy-) ethanewere 59.5 per cent and 30.5 percent of theoretical, respectively,

. --based on the ortho-xenol reacted.

Ewamp le 4 being 79.3 percent of theoretical based. on the meta-xenolreacted. The 1chloro-'2-(metaxenoxy-) ethane is a viscous liquid boilingat approximately 179-181 C. under 5 millimeters pressure and having theformula,

High material, remaining after the above distillation was fnactionallycrystallized from carbon tetrachloride, whereby 62.2grams (0.17

mol) .ofl,2-di-,( meta-xenoxy-.) ethane, was separatedaslwhite.crystalsjfmelting at 128 to 129 0., the yield thereof being15.9 per cent;of theoretical based on the neta-xenol. reacted. Saidproduct has the formula, V

Example 5 A mixture of 170 grams (1 mol) of para-xenol, 99"grams (1 mol)of ethylene chloride, 41.2 grams (1.03 mols). of ,sodium hydroxide, and252 grams of water was heated under reflux at temperatures varying "from.73 to 91 C. for 24 hours. The reaction products were then separated asin Example 2. There were obtained, 78 'grams (0.335 mol) of1-fchloro-2-(para-xenoxy-) ethane as a white crystalline compoundmelting at -;103 C.

andboiling at approximately 163'to 165C. un-

der 3 millimeters pressure, and 7.3 grams (0.02

mol) of l,2-di-(para-xenoxy-) ethane as a white I crystalline compoundmelting. at 219 C. The 1- chloro-2-(para-xenoxy-J ethane and 1,2di-

- (para-xenoxyd ethane have the following respective formulas,

Example 6 I A mixture of 510 grams (3 mols) of ortho-xenol, 381' grams(3 mols) of l,3-dichloro'-isobutane, 123.2 grams-f (3.08 mols) of sodiumhydroxide and 750 grams of water was heated at temperatures between 93and 101..C. under reflux for 10 hours, after which the products wereseparated as in Example 2. There were obtained, 246 grams (1.45 mols) ofunreacted ortho-xenol, 252 grams (0.95 mol) I of.l-chloro-B-(orthoxenoxy-) isobutane and 102.5 grams (0.26 mol) of1,3-di-(ortho-xenoxy-d isobutane. The 1- ch1o ro3(ortho-Xen0xy-)isobutane is a viscous liquid boiling at approximately 170 to 173 C.under 5 millimeters pressure and having the formula,

O-CHzCHCHr-Cl The 1,3-di-(ortho-xenoxy-) isobutane is a more viscousliquid boiling at approximately 280 to reflux at temperatures which weregradually in-' creased from 57 to 72 C. for 5 hours. The mixture wasthen acidified by treatment with a dilute sulphuric acid solution,washed thoroughly with water, and the washings were analyzed todetermine the inorganic bromide content thereof. By this analysis it wasascertained that 58 per cent of the ethylenebromide employed had beenreacted. The product remaining after'the washing operation was distilledwhereby 30 grams of di-(5-secondary-butyl ortho-xenoxy-) distilling attemperatures between 277 and 285 C. at 3. millimeters pressure wascollected. Said product is an extremely viscous yellow-brown l liquid ofspecific gravity 1.043 at 50/4 C., which might be regarded as a softresin when at room temperature. It has probably the formula,

Example '8 A mixture of 205 grams (1 mol) of 3-chloropara-xenol (i. e.3-chloro-4-hydroxy-diphenyl), 94 grams (0.5 mol) of ethylene bromide, 40grams (1 mol) of'sodium hydroxide, and 200 grams of water was heatedunder reflux at temperatures The product is only slightly soluble inboiling benzene. It has probably the formula,

285 C. under 5 millimeters pressure and hav- 2 ing the formula,

Example 7 A mixture of 200 grams (0.89 mol) of 5-secondary-butylortho-xenol (i. e. 2-hydro'xy-5-second ary-butyl diphenyl), 83.6 grams(0.445 mol) of ethylene bromide, 35.6 grams (0.89 mol) of sodiumhydroxide, 37.5 grams of water, and 270 cubic centimeters of methylalcohol was heated under Example 9 A mixture of 452 grams (2 mols) ofS-tertiarybutyl-ortho-xenol (i. e. 2-hydroxy-5-tertiarybutyl diphenyl),80 grams (2 mols)' of sodium hydroxide, 188 grams (1 mol) of ethylenebromide, 84 grams of water, and 600 cubic centimeters of methyl alcoholwas heated under reflux at temperatures between 67 and 73 C. for 16hours, after which the methyl alcohol was distilled from the mixture.The residual material was treated with water, rendered slightly acid bythe addition of dilute aqueous sulphuric acid, and was Washed from thereactor. The mixturewas then extracted with 600 cubic centimeters ofbenzene and the extract was washed thoroughly with Water and distilled.There was collected 125 grams of di-(5-tertiary-butyl-ortho-xenoxy)ethane as ethane Still other dixenyl glycol ethers may be preparedaccording to the procedure hereinbeiore described by using othersubstituted xenols, e. g. 2-hydroxy-5-methyl-xenene, 2-hydroxy-4-ethyl-6-chloro-xenene, 2,2-dichloro-4 hydroxy-xenene, .etc., and otherdihalo-aliphatic hydrocarbons, e. g. a normal butylene chloride orbromide, a normal amyl chloride or bromide, etc., as reactants. In sofar as we are aware, any xenol containing no strongly acidic or basicradical may be reacted with any saturated dihalo-aliphatic hydrocarboncontaining chlorine and/or bromine as the halogen substituents, andhaving the halogen atoms situated on two different primary or secondarycarbon atoms to form the corresponding dixenyl glycol ether.

ther modes of applying the principle of the invention may be employedinstead of those ex,

plained, change being made as regards the method or compounds hereindisclosed, provided the steps or compounds stated by any of thefollowing claims or the equivalent of such stated steps or compounds beemployed.

r We therefore particularly point out and dis-. tinctly claim: as ourinvention:

v 1;. A di-xenyl glycol ether.

. 2. A compound havingthe general formula,

wherein R is a substituent of the group consisting of hydrogen and alkylradicals, n is an integer, and each xenoxy radical is attached to acarbon atom (selected from the class consisting of primary and secondarycarbon atoms) of the aliphatic radical. I

3. 1,2-di-.(ortho-xenoxy-) ethane.

4. 1,2-cli- (meta-xenoxy-) ethane.

5. 1,2-di-(para-xenoxy-) ethane.

'6. In a method of making dixenyl glycol ether, the step which consistsin heating an alkali metal xenate to a reaction temperature withapproximately one-half "of its molecular equivalent of a saturateddihalo-aliphatic hydrocarbon having the general formula, X-CH(R) CnHZn-Zwherein R is a substituent] of the group consisting of hydrogen andalkyl radicals, n is an integer, X and Z represent halogen substituentsselected from the class consisting of chlorine and. biomine, and thehalogen substituent Z is attached to a carbon atom of the classconsisting of primary and secondary carbon atoms.

GERALD H. COLEMAN. LINDLEY E. MILLS. GARNETT V. MOORE.

